Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
  • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
  • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
  • C07C45/46—Friedel-Crafts reactions
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
  • C07C45/47—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation using phosgene
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
  • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
  • C07C65/32—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing keto groups
  • C07C65/40—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing keto groups containing singly bound oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule

Definitions

• This invention relates to a method of preparing arylene ketone oligomers and arylene sulphone oligomers and in particular to an electrophilic process for pre­paring such oligomers.
• Arylene ketone and arylene sulphone oligomers, in particular arylene ether ketone oligomers are useful inter alia as so-called hard blocks in the preparation of di-, tri-or multi-segment block copolymers.
• the hard blocks may contain as many as 100 repeat units, whilst for multi-segmented block copolymers the hard blocks may contain form 10-30 repeat units.
• They are also useful in the preparation of flame retardants, antioxi­dants and ultraviolet light stabilisers. This inven­tion is directed to an improved electrophilic synthesis for preparing such oligomers, in particular para-linked oligomers.
• the oligomerisation step involves the formation of an aryl ketone or sulphone group from a carboxylic or sulphonic acid or acid derivative group and an aromatic compound con­taining an aromatic carbon bearing an activated hydro­gen atom, i.e., a hydrogen atom displaceable under the electrophilic reaction conditions.
• the monomer system employed in the polymerisation can be, for example,
• Electrophilic reactions of this type are referred to as Friedel-Crafts oligomerisation reactions.
• oligomerisations are carried out in an anhydrous reaction medium comprising the reactant(s), a catalyst, such as anhydrous aluminium trichloride, and solvent such as methylene chloride, carbon disulfide, nitromethane, nitrobenzene, or ortho-dichlorobenzene, or mixtures thereof.
• the aluminium trichloride catalyst is generally employed in an amount greater than one equivalent for each equivalent of carbonyl or sulphonyl groups in the reac­tion medium.
• Other inorganic halides such as ferric chloride, may be employed as the catalyst.
• Patents No. 971,227 and 1,086,021 disclose the preparation of poly(arylene ketones) by Friedel-Crafts polymerisation and generally acknowledge some of the difficulties in producing tractable, melt-­stable products.
• One criterion for choosing the controlling agent in this process is that it should not be an acylating or alkylating agent, nor should it be acylatable under the reaction conditions. It is known that protic com­pounds act as acylating or alkylating agents in Friedel-Crafts reactions in the presence of aluminium trichloride.
• succinic acid and benzoic acid have proved particularly useful in this respect. It cannot be reliably predicted whether a particular controlling agent will act as a dispersant, since this appears to depend on the other materials present and their relative properties and reaction con­ditions, but the dispersant effect is readily recognised (and reproduced once recognised) by suitably skilled operators. It has also been discovered that water can be added as the controlling agent, contrary to the well-known requirement for substantially anhydrous conditions in Friedel-Crafts reactions.
• the present invention provides in one aspect a method of preparing an arylene oligomer having the repeat unit: -Ar-O-Ar-B- where each B independently is a carbonyl (-CO-) or sulphonyl (-SO2-) group, and each Ar is independently a substituted or unsubstituted phenylene moiety or a substituted or unsubstituted poly­nuclear moiety, aromatic carbon atoms of which are bonded directly to the -O- ­or -CO- or -SO2- groups, which comprises oligomerising a monomer system comprising (I) phosgene or an aromatic or aliphatic carboxylic or sulphonic diacid dihalide monomer and a polynuclear aromatic comonomer having two activated hydrogens or (II) a self-oligomerising polynuclear aro­matic monomer containing both a carboxylic or sulphonic acid halide group and an active hydrogen
• the present invention provides a method of producing an arylene oligomer which compri­ses oligomerising a monomer system comprising:
• the process of the present invention enables substantially linear arylene oligomers to be prepared using as a controlling agent a generally cheap and easily available compound (or compounds) which is rela­tively non-hazardous.
• This invention is especially concerned with preparation of the aromatic oligomers having an inherent viscosity of less than about 0.6 and having at least 2 repeat units.
• inherent viscosity refers to the mean inherent viscosity determined according to the method of Sorenson et al, "Preparative Methods of Oligomer Chemistry" Intersience (1986), at page 44 [0.2 g oli­gomer dissolved in 100 ml of concentrated sulfuric acid at 25°C].
• R in the controlling agent (B) is compatible with the monomer(s) and the other components of the reaction medium in the sense that it does not unacceptably interfere with the reaction.
• R may be any desired monofunctional or (where appropriate) difunctional aliphatic aromatic or hetero­cyclic group, for example a substituted or unsubsti­tuted alkyl, alkylene, aryl, arylene, alkaryl or aralkyl group.
• Simple aliphatic or aromatic groups are preferred, especially alkyl and alkylene groups, pre­ferably n-alkyl and n-alkylene groups, and phenyl or naphthyl groups or phenylene or naphthylene groups.
• the controlling agent may be an alcohol ROH, which also includes diols HOROH, or an organic metal oxide where X is, for example, an alkali metal such as sodium.
• ROH an alcohol
• X an alkali metal such as sodium
• Unbranched alcohols e.g. n-­alkanols, are preferred, especially the n-lower alka­nols, e.g. n-butanol.
• controlling agent is of the formula R(COOX) a as defined above, this may be a carboxylic acid R-COOH, which includes dicarboxylic acids XOOC-R-COOX, or metal salts thereof where X is, for example an alkali metal.
• Y is preferably a di- or trivalent metal atom and b is 2, 3 or 4 respectively e.g. (RO)3Al, (RO)4Ti, (RO)2Zn.
• R is a substituted or unsubstituted aryl group, or linear or branched alkyl group, or their arylene or alkylene equivalents where appropriate. More preferably R is an unsubstituted alkyl group espe­cially a C1-C5 alkyl group, e.g. a methyl, ethyl, pro­pyl, isopropyl, n-butyl or isobutyl group; or an unsubstituted aryl group, e.g. a phenyl or naphthyl group, and preferably aryl R groups are deactivated to electrophilic attack by attachment of electron-­withdrawing groups.
• controlling agents have fewer than 8 aliphatic carbon atoms, or even fewer than 5 aliphatic carbon atoms, directly bonded to one another, this including the possibilities that only one or no aliphatic carbon atoms are present, or that fewer than the stated numbers of such atoms are present in any one group, in the controlling agent molecule.
• Suitable controlling agents include methanol, ethanol, isopropanol, butanol, acetic acid, propionic acid, butanoic acid, trich­loroacetic acid, trifluoroacetic acid, methane sulpho­nic acid, succinic acid, sodium methoxide, sodium ethoxide, (CH3CH2O)3Al, (CH3COO)3Al, pentafluorophenol, and benzoic acid.
• trifluoroacetic acid may have the useful ability to produce a very fast reaction, or alternatively to reduce the amount of alu­minium chloride needed for a given reaction speed possibly because the electron-withdrawing effect of the fluorine atoms produces a more highly charged aluminium atom in the resulting Lewis acid/controlling agent complex.
• Mixtures of two or more controlling agents may be used if desired, and mixtures of the present protic controlling agent(s) with the non-protic Lewis base controlling agents described in the aforementioned European Patent Application 0124276 (whose disclosure is incorporated herein by reference) may be helpful.
• Methanol controlling agent plus sulpholane Lewis base is one example of such a mixture.
• the controlling agent acts, inter alia, to suppress undesirable side reactions, particularly ortho substitution of the aromatic rings in the monomer system.
• the aroma­tic rings which are particularly susceptible to ortho substitution are active aryloxy groups.
• Such groups are referred to herein as undeactivated aryloxy groups.
• undeactivated aryloxy group is meant an aryloxy group which is in a molecule in which there are no deactivating groups or is located at least two aromatic moieties (i.e. Ar as defined above) away from a deac­tivating group such as a carbonyl.
• a "deactivated aryloxy group” is an aryloxy group separated from a deactivating group, usually carbonyl, by an aromatic group containing one aromatic ring, fused aromatic rings or aromatic rings linked by direct bonds. Suppression of side reactions results in a oli­gomer that is thermally stable, that is it does not degrade or cross-link when subjected to elevated tem­peratures, for a period of time. For an oligomer of this type to be suitable for melt processing, it must be able to withstand the processing temperatures for the required processing time.
• oligomers typically withstand tem­ peratures up to about 30°C above the melting or softening point of the oligomer for periods of at least 30 minutes, preferably at least 60 minutes and most preferably at least 90 minutes, without undesired gel formation or substantial change in inherent viscosity.
• heat-reactive oligomers will be desirable for further reaction in their subsequent uses.
• the amount of controlling agent present is pre­ferably from 0.1 to 4 equivalents per equivalent of acid halide groups present in the monomer system. Amounts greater than 4 equivalents could be employed, if desired. However, no additional controlling effect is usually achieved by adding larger amounts. Thus, it is preferred to use no more than 4 equivalents, more preferably between 0.5 and 4 equivalents and especially between 0.5 and 2 equivalents per equivalent of acid halide groups.
• the actual amount of controlling agent added depends upon, inter alia, the particular controlling agent used, the nature of the monomers pre­sent and the type and amount of Lewis acid employed.
• the controlling agent acts to control the reaction, it is believed that one or more of the following factors may be involved. It is thought that the controlling agent forms a complex or compound (hereinafter "complex" for simplicity) with the Lewis acid. The complex appears to act as a solvent for the oligomer-Lewis acid complex formed during the reaction thereby maintaining the oli­gomer in solution or in a reactive gel state and in some cases producing a dispersion of the resulting oli­gomer. Further, the reaction mixture is more trac­ table, making work up of the oligomer easier and ensuring effective removal of catalyst residues during purification.
• complex complex or compound
• the solubilization property of the Lewis acid/controlling agent is particularly significant in the preparation of para-linked arylene ether ketone oligomers.
• the controlling agent is selected such that, usually in complex form with the Lewis acid, it maintains the resulting oligomer in solution, at least until a desired molecular weight is reached, and may con­veniently produce a dispersion of the oligomer. Whether a controlling agent will maintain the eventual oligomer in solution/gel or disperse it can be readily determined by experiment.
• Lewis acid is used herein to refer to a substance which can accept an unshared electron pair from another molecule.
• Lewis acids which can be used in the practice of this invention include, for example, aluminum trichloride, aluminum tribromide, antimony pentachloride, antimony pentafluoride, indium trich­loride, gallium trichloride, boron trichloride, boron trifluoride, zinc chloride, ferric chloride, stannic chloride, titanium tetrachloride, and molybdenum pen­tachloride.
• substantially anhydrous alumi­num trichloride as the Lewis acid is preferred.
• the amount of Lewis acid used in the practice of this invention varies depending on the particular mono­mers and reaction medium selected. In all instances at least about one equivalent of Lewis acid per equivalent of carbonyl groups present in the monomer system is used plus one equivalent per equivalent of controlling agent used plus an amount effective to act as a cata­ lyst for the polymerisation (also referred to herein as a catalytic amount). Generally a catalytic amount added is from about 0.05 to about 0.5 equivalents of Lewis acid per equivalent of acid halide in the reac­tion mixture. When aluminium chloride is used as the Lewis acid one equivalent is considered to be AlCl3. Further, if a comonomer containing other basic species, such as sulfone groups, is used, additional Lewis acid may be required.
• a non-protic diluent can also be employed, if desired, "non-protic" meaning that the diluent has no hydrogens directly bonded to oxygen or nitrogen.
• Such diluents are also known as “aprotic”.
• the diluent should dissolve the Lewis acid/controlling agent complex and the resulting oligomer/Lewis acid complex. It should also be relatively inert toward Friedel-Crafts reactions.
• the diluent is preferably somewhat polar as measured by its dielectric constant and solubility parameter.
• the dielectric constant of the diluent is at least about 2.0 at 24°C, and preferably in the range of from about 4.0 to about 25 at 24°C.
• the Hildebrand solubility parameter of the diluent is preferably at least about 7.2 [cal/cm3] 1 ⁇ 2 and is preferably in the range of from about 9.2 to about 15 [cal/cm3] 1 ⁇ 2 .
• Preferred diluents include, for example, methylene chloride, carbon disulfide, o-dichlorobenzene, 1,2,4-trichlorobenzene, o-difluoro­benzene, 1,2-dichloroethane, cyclohexane, 1,1,2,2,-tetrachloroethane and mixtures thereof.
• the diluent is used in an amount from 0 to about 93% by weight, based on the weight of the total reac­tion mixture.
• the reactions can be run without the presence of a diluent.
• the diluent is used in an amount of at least about 10%, preferably at least about 20% by weight of the reaction mixtures.
• Alkylene ketone oligomers contain arylene and ketone groups and may also contain additional groups in the oligomer chain, including, for example, ether, sulfone, sulfide, amide, imide, azo, alkylene, perfluoroalkylene and other appropriate groups.
• arylene sulfone oligomers contain arylene and sulfone groups in the oligomer optionally with other linkages.
• the monomer system comprises: (a) an aromatic compound containing a carboxylic or sulfonic acid derivative and an active hydrogen atom being acti­vated toward electrophilic displacement by, for example, an electron donating group situated ortho or para with respect to said hydrogen atom; or (b) a two-­monomer system of a dicarboxylic or disulfonic acid derivative group and an aromatic compound containing two such displaceable active hydrogen atoms.
• active hydrogen atom refers to a hydrogen atom bound to an aromatic carbon atom, i.e. a carbon atom which is part of an aromatic ring
• poly­nuclear aromatic moieties is used to mean aromatic moieties containing at least two aromatic rings.
• the rings can be fused, joined by a direct bond or by a linking group.
• at least two of the aromatic rings are linked by an ether oxygen linkage.
• Other linking groups which can join aromatic rings in the aromatic moieties include for example, ether, carbonyl, sulfone, sulfide, amide, imide, azo, alkylene, perfluoroalkylene and the like.
• the phenylene and polynuclear aromatic moieties contained in the monomers can contain substitutents on the aromatic rings. Such substitutents should not inhibit or otherwise interfere with the polymerisation reaction to any significant extent.
• Such acceptable substitutents include, for example, phenyl, halogen, ester, nitro, cyano, alkyl and the like.
• aromatic diacid dihalide is preferably a dichloride or dibromide.
• suitable diacid dihalide monomers, polynuclear aromatic comonomers which can be used with such diacid dihalide monomers, and self-polymerising acid halide monomers are described in the aforementioned European Published Patent Application 0178871, the disclosure of which is incorporated herein by reference.
• monomers which do not contain an ether linkage can be employed as long as one or more of the monomers used contains at least one ether oxygen linkage, for example Ph-O-Ph-SO2-Ph-O-Ph, or Ph-O-Ph-C(CH3)2-Ph-O-Ph, wherein Ph represents a p-­phenylene unit, which can be used as the sole monomer with an ether containing diacid dihalide or with phos­gene or any diacid dihalide when used in addition to a polynuclear aromatic monomer.
• ether oxygen linkage for example Ph-O-Ph-SO2-Ph-O-Ph, or Ph-O-Ph-C(CH3)2-Ph-O-Ph, wherein Ph represents a p-­phenylene unit, which can be used as the sole monomer with an ether containing diacid dihalide or with phos­gene or any diacid dihalide when used in addition to a polynuclear
• the molecular weight of the oligomer, the degree of branching and amount of gelation can be controlled by the use of, for example, capping agents as described in U.S. Patent No. 4,247,682, the disclo­sure of which is incorporated herein by reference.
• the molecular weight of the oligomer can also be controlled in a reaction utilizing a two-monomer system as described above, by employing a slight excess of one of the monomers.
• the temperature at which the reaction is conducted can be from about -50°C to about +150°C. It is pre­ferred to start the reaction at lower temperatures, for example at about -50°C to about -10°C particularly if the monomer system contains highly reactive monomers. After reaction has commenced, the temperature can be raised if desired, for example, to increase the rate of reaction. It is generally preferred to carry out the reaction at temperatures in the range of between about -30°C and +25°C.
• Capping agents when employed, are added to the reaction medium to cap the oligomer on at least one end of the oligomer chain. This terminates continued growth of that chain and controls the resulting molecu­lar weight of the oligomer, as shown by the inherent viscosity of the oligomer. Judicious use of the capping agents results in a oligomer within a selected narrow molecular weight range, decreased gel formation during oligomerisation, and decreased branching of the oligomer chains and increases oligomer stability. Both nucleophilic and electrophilic capping agents may be used to cap the oligomer at each end of the chain.
• Preferred nucleophilic capping agents are 4-chlorobiphenyl, 4-phenoxybenzophenone, 4-(4-phenoxy­phenoxy)benzophenone, biphenyl 4-benzenesulphonylphenyl phenyl ether, and the like.
• Typical electrophilic capping agents are compounds of the formula Ar-CO-E or Ar-SO2-E wherein Ar ⁇ is phenyl, 3-chlorophenyl, 4-chlorophenyl, 4-cyanophenyl, 4-methylphenyl or an aromatic group substituted with an electron withdrawing substitutent and E is halogen or other leaving group.
• Preferred electrophilic capping agents include benzoyl chloride, benzenesulfonyl chloride and the like.
• the Lewis acid/controlling agent complex apparently solubilizes or solvates the oligomer so that it remains in the reaction medium in a form capable of sustaining reaction to the desired molecular weight in a controlled and reproducible fashion either as a solution/gel or as a dispersion.
• Lewis acid is also present in the reaction medium as the catalyst for the Friedel-Crafts polymerisation reaction.
• the resulting oligomer contains Lewis acid complexed to the carbonyl groups of the oligomer.
• the Lewis acid is complexed to substantially all the carbonyl groups in the oligomer, and this catalyst residue must be removed, i.e the Lewis acid must be decomplexed from the oligomer and removed.
• a method for removing the catalyst residue is described in U.S. Patent No. 4,237,884 the disclosure of which is incorporated herein by reference.
• Decomplexation can be accomplished by treating the polymerisation reaction mixture with a decomplexing base after completion of polymerisation.
• the base can be added to the reaction medium or the reaction medium can be added to the base.
• the decomplexing base must be at least as basic towards the Lewis acid as the basic groups on the oligomer chain. Such decomplexation should be effected before isolation of the oligomer from the reaction mixture.
• the amount of decomplexing base used should be in excess of the total amount of bound (complexed) and unbound Lewis acid present in the reaction mixture and is preferably at least twice the total amount of Lewis acid.
• Typical decomplexing bases which can be used include water, dilute aqueous hydrochloric acid, metha­nol, ethanol, acetone, N,N-dimethyl-formamide, N,N-dimethylacetamide, pyridine, dimethyl ether, diethyl ether, tetrahydrofuran, trimethylamine hydroch­loride, dimethyl sulfide, tetramethylenesulfone, ben­zophenone, tetramethylammonium chloride, isopropanol and the like.
• the decomplexed oligomer can then be removed by conventional techniques such as adding a nonsolvent for the oligomer which is a solvent for or miscible with the Lewis acid/controlling agent complex and Lewis acid; spraying the reaction medium into a nonsolvent for the oligomer; separating the oligomer by filtration; or evaporating the volatiles from the reac­tion medium and then washing with an appropriate solvent to remove any remaining complex and diluent from the oligomer.
• a nonsolvent for the oligomer which is a solvent for or miscible with the Lewis acid/controlling agent complex and Lewis acid
• spraying the reaction medium into a nonsolvent for the oligomer separating the oligomer by filtration; or evaporating the volatiles from the reac­tion medium and then washing with an appropriate solvent to remove any remaining complex and diluent from the oligomer.
• the I.V. of the material measured as a 0.2% solu­tion in 98% sulphuric acid was 0.24 dl/g.
• the oligomer was isolated using the method out­lined in Example 1.
• the oligomer thus obtained had an inherent visco­sity of 0.36 dl/g as measured in a 0.2% solution of 98% sulphuric acid.
• the structure of the oligomer was con­firmed by 13C n.m.r. spectroscopy.
• the resultant oligomer had an inherent viscosity of 0.32 dl/g as measured in a 0.2% solution in 98% sulphuric acid.
• the resultant oligomer had an inherent viscosity of 0.23 dl/g as measured in a 0.2% solution in 98% sulphuric acid.
• the structure of the oligomer was confirmed by 13C n.m.r. spectroscopy.

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• 1986
  • 1986-09-30 GB GB868623511A patent/GB8623511D0/en active Pending
• 1987
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  • 1987-09-29 EP EP87308609A patent/EP0262920B1/de not_active Expired - Lifetime
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